2-hydroxy-1,1,2,3,3-pentahydro-perfluoroalkyl derivatives

ABSTRACT

A 2-hydroxy-1,1,2,3,3-pentahydroperfluoroalkyl derivative of either one of the formulae:

United States Patent Katsushima et al.

Z-HYDROXY-1,l,2,3,3-PENTAHYDRO- PERFLUOROALKYL DERIVATIVES Inventors: Atsuo Katsushima; Iwao Hisamoto;

Shoshin Fukui; Chiaki Maeda; Akitoshi lwatani; Takahisa Kato; Masayuki Nagai; Hiroyuki Shinkai, all of Osaka; Masayuki Asaoka, Kyoto, all of Japan Assignee: Daikin Kogyo Co. Ltd., Osaka,

Japan Filed: Oct. 24, 1972 Appl. No.: 299,741

Related US. Application Data Continuation-in-part of Scrv No. 877,497, Nov. 17, 1969, abandoned.

Foreign Application Priority Data Nov. 18, 1968 Japan 43-84276 Dec. 5, 1968 Japan 43-89252 Dec. 19, 1968 Japan 43-93513 Dec. 19, 1968 Japan 43-93514 Feb. 7, 1969 Japan 44-9524 Mar. 10, 1969 Japan 44-18411 Scpl. I8, 1969 Japan 44-74146 Mar. 11, 1975 [56] References Cited UNITED STATES PATENTS 3,459,788 8/1969 Enoki et al. 260/475 P 3,461,154 8/1969 LaFont et a1 3,504,016 3/1970 Smeltz 260/475 F 3,624,139 11/1971 Gilbraltar et a1 260/486 B 3,641,112 2/1972 lchikawa et al. 260/475 P Primary E.raminerLorraine A. Weinberger Assistant Examiner-E. Jane Skelly Attorney, Agent, or FirmBierman & Bierman [57] ABSTRACT A 2-hydroxy-l,l,2,3,3pentahydroperfluoroalkyl derivative of either one of the formulae:

[RfCH CH(OH )CH OOC l "IQ and Q I 2)IH wherein Rf is a perfluoroalkyl, an w-hydroperfluoroalkyl or an w-chloro-perfluoroalkyl group having 4 to 20 carbon atoms, Q is a hydrocarbon residue having a valency corresponding to m which may contain one or more of -COO and OH in and/or on the chain, O is a hydrogen atom or a hydrocarbon residue having a valency corresponding to m which may contain one or more of O, COO, NH-, N and in the chain, R and R are each a hydrogen atom or a group of the formula: CH CH(OH)CH Rf, at least one of R and R being CH CH(OH)CH Rf, m is an integer of not less than 2 and m is an integer of not less than 1, which is useful as an oil-repellent agent or an anti-soiling agent for fibrous materials.

5 Claims, No Drawings 1 2 Z-HYDROXY-l,l,2,3.3-PENTAHYDRO- eliminated upon laundering. This method, however, PERFLUOROALKYL DERIVATIVES fails to prevent soil attachment itself. Further, for instance, fabrics are treated with a solution or dispersion This is a continuation-in-part application of our coof polymers of CgF17SOgN(C- IH5)CH- 1C pending application Ser. No. 877,497, filed Nov. 17, 5 H OOCCH=CH or C H CH CH OOCC(CH )=CH I969, now abandoned. or of chromic acid compounds having a polyfluoroalkyl The present invention relates to 2-hydroxy-l,l,2,3,3- group such as C F COOCr (OH)Cl to impart oilpentahydro-perfluoroalkyl derivatives, and their prorepellent property to them whereby the attachment of duction and use. More particularly, it relates to new oily and aqueous stains is prevented. However. it is and useful 2-hydroxy-l,l,2,3,3-pentahydro- I( quite difficult to remove the once attached stain by perfluoroalkyl derivatives, to compositions containing laundering. and stained parts increase during laundersame suitable for treating fibrous materials to render ing by adsorption and preservation of soils contained in them oleophobic and anti-soiling, and to fabrics and fiwashings on the surface of the fabrics. bers which have been sized or coated with the same so It has now been found that the perfluoroalkyl comas to have been rendered oleophobic and anti-soiling. l5 POUnd 0f e in entio Can impart excellent Oil- The perfluoroalkyl compounds of the present invenrepellent and anti-soiling properties to fibrous materition can be classified into two groups, Le, als'treated therewith. Aqueous and oily soils will not I. Carboxylic ester compounds f th f l readily attach to the treated fibrous materials and, even if attached, can be readily and completely eliminated lRfCH'lCH(OH)CH2OOC]mQ by conventional laundering techniques. Thus, the per- HA] fluoroalkyl compounds of the invention are useful as oil-repellent agents and antisoiling agents. In addition, they are useful as plasticizers and also as intermediates for fluorine-containing polyurethanes.

The carboxylic ester compounds [IA] can be produced by reacting a perfluoroalkylpropylene oxide of the formula:

wherein Rf is a perfluoroalkyl group, an w-hydroperfluoroalkyl group or an w-chloro-perfluoroalkyl group having 4 to 20 carbon atoms, 0 is a hydrocarbon residue having a valency corresponding to m which may contain one or more of -O-, -COO and -OH in and/or on the chain and m is an integer of not less than 2; abd RfCH CHCH 2 Amine com ounds of the formula P t 0 [II] OI( 1 2)m Bl wherein Rf is as defined above with a reagent ofthe for- 15 mula: wherein O is a hydrogen atom or a hydrocarbon resi- OH due having a valency corresponding to m which may contain one or more of O, COO, -NH, [ml -N= and wherein Q and m are each as defined above.

. The epoxide [ll] may be prepared, for instance, by

CHZQHWHMH Rf adding radically a perfluoroalkyl iodide of the formula:

- Rfl wherein Rf is as defined above to allyl alcohol and treating the resultant alcohol of the formula:

in the chain, R, and R are each a hydrogen atom or a RfcH CHlCH OH wherein Rf is as defined above with group of the formula: -CH CH(OH)CH Rf, at least an alkali hydroxide (e.g. sodium hydroxide, potassium one of R and R being CH CH(OH)CH Rf, m is an hydroxide) in water to eliminate hydrogen iodie thereinteger of not less than 1 and Rf is as defined above. from. Examples of the epoxide [ll] are as follows:

Hitherto, there have been proposed various methods Th reagent [III] i carboxylic acids having a basicity for imparting anti-soiling property to fibrous materials. f not l h 2, d preferred examples are as f l- For instance. fabrics made of hydrophobic synthetic l fibers or fabrics processed with a hydrophobic syni a dib i carboxylic acid of the formula: thetic resin are treated with a solution or suspension of a hydrophilic substance such as polymers having 5 O(COOH)2 acrylic acid as the unit constituent, polyethylene glycol wherein Q. is a divalent hydrocarbon residue such as derivatives and carboxymethyl cellulose. As a result of -(CH wherein p is an integer of l to 4,

such treatment, soils attached to the fabrics can be -CH=Q l-l or -C6H4 (e.g. malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid, phthalic acid);

ii. an acid having a basicity of more than 2 (e.g. pentane-l ,3,3,5-tetracarboxylic acid, mellitic acid, pectinic acid, alginic acid, hemimellitic acid, trimellitic acid, benzenepentacarboxylic acid, citric acid, aconitic acid, trimesic acid, polyacrylic acid);

(iii) a dicarboxylic acid containing polyethylene oxide chain of the formula: HOOCAO(CH CH O) ACOOH wherein ACOO- is RCOO- --COCH=CHCOO or COCH=CHCOO(Cl-l2CH2O)rCOCH= CHCOO- in which R is a divalent hydrocarbon group and q and r are each an integer of not less than 1 (e.g. HOOCCH CH O(CH2CH2O),,- CH CH COOH, HOOCCH2O(CH2CH2O),,- CHzCOOH, HOOCCH=CHCOO(CG CH2- O),,COCH==CHCOOH, HOOCCH=CHCOO- (CH CH O),,COCH=CHCOO(CH CH O),,- COCH=CHCOO(CH CH2O)COCH= QQHL .COOH 4-140) 4 get-coon +RfCH CHCH d-cooca cmomcn af II [II] [IA wherein d) is the residue of a carboxylic acid excluding -COOH therefrom and Rf is as defined above.

As the carboxylic acid [llla] is, in most cases, soluble in water and apt to be removed from the reaction mixture, it is prefered to be employed in a slightly excess amount. The epoxide [ll] is normally liquid at room temperature, and the reaction may be carried out without using any solvent. The carboxylic acid [llla] has generally a melting point higher than 80C, and the reaction is favorably carried out at a temperature higher than 80C. The reaction rate is in general markedly suppressed at a temperature lower than 80C. although it is more or less associated with the kind of the carboxylic acid [Illa]. The addition ofa base such as an alkali metal hydroxide (e.g. sodium hydroxide, potassium hydroxide) or a tertiary amine (e.g. triethylamine) as a catalyst to the reaction system may result in the acceleration of the reaction rate. The yield of the carboxylic ester compound [lAa] in the reaction is excellent and nearly quantitative.

Examples of the carboxylic ester compound [lAa] obtained by the reaction using the carboxlyic acid [Illa] include:

the ester of alginic acid of 70 to 120 in polymerization with F(CF CF CH C\H/CH wherein r, r and r" are each an integer of 2 to 10, s, s, s" and s" are each an integer of0 to and t, t and I" are each an integer of 3 to 20.

The amine compound [18] can be produced by reacting a perfluoroalkylpropylene oxide of the formula:

RfCH CHCH degree of mine, hexamethylenediamine, pentaethylenehexamine, melamine, octadecylamine, hexamethylenetetramine, aniline, diethylenetriamine, triethylenetetramine, cyclohexylamine, benzylamine, benzylaniline and an amine containing polyethylene oxide chain of the formula: R"HNRO(CH CH O),,RNHR" wherein R" is a hydrogen atom or an alkyl group and R and p are each as defined above (e.g. H N(CH O(CH C- COO- NHCH H NCH The reaction between the epoxide [H] and the primary amine llVa] proceeds as follows:

7 8 try-m arcn onca Q5'NHCH CH(OH)CH Rf [Iva] [II] [IBa] '-NHCH CH(OH)CH Rf arcn cnca l 0 [II] I /OH CH(OH)CH Rf '-N wherein d) is the residue ofa primary amine excluding (e.g. triethylamine). The reactions are normally comz therefrom and Rf is as defined abOVe- Thus, the pleted in 30 minutes to hours to give the perfluororeaction of the epoxide [II] with the primary amine alkyl compound [lBa] [18:2] in nearly quantitative [lVa] an equimolar amounts affords the secondary yields. The thus obtained perfluoroalkyl compound amine [18a] and, when the epoxide [ll] is employed in [lBa] [IBe] may be further converted into its acid adtwo molar amount to one molar amount of the primary dition salt by treatment of the former with an organic amine [Iv there i b i d h tertiary amine 20 or inorganic acid usually at a temperature from room [[B Th reaction between h id [1]] d th temperature to 100C, if desired, in an inert organic secondary amine [IVb] is represented by the formulae; solvent such as fluoralkanes. This conversion is advatagla RIE'CH2CHCH2 gii pnca catomca nr J wherein d)" is the residue ofa Secondary amine excludgeously out ely after completion of mg therefrom, is the residue of a thereaction between the epoxide [Ill and the primary Ondary amine excluding H therefrom and Rfis amine [lVa] the secondary amine [NM or ammonia as d fi d abOVe In place of the primary amine [Wu] [lVc], |.e. without the isolation of the produced perfluor the secondary amine [lVb], there may be used amoroalkyl Compound [IBal [[89] from the reilctlon monia [lVc], which is reacted with the epoxide [II] as mixtljlre T.He.perfluor(.)alkyl.conlpqund 7 Belit' follows: self IS a liquid or solid which IS insoluble in water,

[No] [II] [IBc] H NCH CH(OH)CH Rf RfCH CHCH -I-INCH CH(OH)CH Rf [Die] 0 [II] CH CH(OH)CH Rf [IBd] a cmomoa nr HNCH CH(OH)CH Rf RfCH CHCH N-CH CH(OH)CH Rf CH CH(OH)CH Rf [13d] 0 [II] CH CH(OH)CH Rf [IBe] All the above reactions are usually effected by treatwhereas most of its acid-addition salts are soluble in ing the epoxide [ll] with the primary amine [lVa], the water. Both are utilizable for the object of this invensecondary amine [IVb] or ammonia [We] in a slightly tion. excess amount at a temperature from 30 to 150C. The produced perfluoroalkyl compound [lBa] preferably from to C. The use of a solvent is [IE9] is falle in o of th following formula not always needed. If employed, the use of an inert organic solvent such as fluoroalknes is recommended for controlling the elevation oftemperature caused by generation of heat. in general the presence of water in the reaction system is unfavorable. and its amount should RfcH be suppressed to not more than 10% by weight. The re- 2 actions can be promoted by the use of a tertiary amine RCH CH(0H)GH 3,870, 9 RfCH CH( OH CH2\N CH Cm OHWH Rf RfCH CH(OH)CH 2 2 wherein X and X are each a hydrogen atom or a hydrocarbon group bearing or not one or more substituents. Spceific examples are as follows:

with diethylenetriamine As stated above. the pcrfluoroalkyl compound [IA] or [IB] (including the acid addition salt) have oleophobic and anti-soiling properties. Based on such proper- 35 ties, they are used for treatment of fibrous materials.

On treating fibrous materials with the perfluoroalkyl compound [IA] or [IE] (including the acid addition salt), the active ingredient is dissolved or dispersed in a suitable solvent to make 0.05 to 5 by weight con- 40 centration, the fibrous materials are immersed therein and the wet materials are dried in atmosphere or while heating at 80 to 150C for 30 seconds to minutes.

As the solvent, the use of an organic solvent having a boiling point from to 150C, particularly from 5 to 100C, is preferred. Specific examples of such organic solvent are fluoroalkanes (e.g. trichlorotrifluoroethane, dichlorotetrafluoroethane), ketones (e.g. acetone, methyl ethyl ketone), esters (e.g. ethyl acetate), fluorine-containing cyclic compounds (e.g. benzotrifluoride), etc. For dilution of these solvents, there may be also used benzene, petroleum ether, xylene or the like.

From the economical viewpoint, it is advantageous to make up an aqueous dispersion. Thus, the active ingredient is dispersed in water in the presence of an appropriate emulsifier by conventional operations. Examples of the emulsifier are anionic surfactants (e.g. sodium dodecylbenzenesulfonate, C F COONa), non-ionic surfactants (e.g. polyoxyethylenealkyl phenyl ether, polyoxyethylenc amyl ester, sorbitan fatty acid ester), cationic surfactants (e.g. quaternary ammonium salts),

etc.

The textile fabrics treated with the anti-soiling treatments of this invention are quite excellent in repellency ,5 to stains, stain-removing actions, prevention of soil redeposition during laundering and durability to laundering and show very favorable appearance.

The perfluoroalkyl compound [IA] or [IB] (including the acid addition salt) is also used for the separation of water and oil (e.g. kerosene, sesame oil. heavy oil, machine oil, watch oil, refrigerator oil, hexane, heptane, octane, cyclohexane) from their mixture. For instance, porous materials such as paper, woven fabric. non-woven fabric and asbestos are treated with the active ingredient dissolved or dispersed in water or organic solvents, if necessary, by the aid ofsurfactants so that the porous materials are imparted oil-repellency and allows only the passing of water therethrough.

The perfluoroalkyl compound [IA] or [IE] (including the acid addition salt) may be also employed in combination with any water-phobic agent. In such case, the materials treated with them are imparted both oilrepellency and water-repellency. Examples of the water-phobic agent are the polymers of the fluorinecontaining vinylcarboxylic esters of the formula: RfCI-I CH(OH)CH OOCCR =CHhd 2 wherein R is a hydrogen atom or a methyl group. The vinylcarboxylic esters may be produced, for instance, by reacting the epoxide of the formula:

Rf CH CH/CH 2 or the diol of the formula:

RfCH CH(OH)CH OH with acrylic acid or methacrylic acid. The ratio by weight of the perfluoroalkyl compound [IA] [[8] and the vinylcarboxylic ester is 9:l 1:9, favorably 5:1 1:5. On treatment, these active ingredients are employed in the form of solution or dispersion in water or organic solvents, if necessary, by the aid of surfactants.

In addition to the above uses, the perfluoroalkyl compound [IA] or [IE] including the acid addition salt) may be used as plasticizers or intermediates for the synthesis of polyurethanes. For instance, the diol of the formula:

wherein Y is a hydrocarbon group bearing or not one or more substituents or its mixture with an active hydrogen-containing material such as ethyleneglycol adipate, propyleneglycol adipate, condensates of w-hydroxyhexanoate or glycerol adipate is polymerized with a diisocyanate of the formula: OCNYNCO wherein Y is a hydrocarbon group (e.g. 2,4- or 2,6- tolylenediisocyanate, 3,3-bitolylene-4,4'-diisocyanate, diphenylmethane-4,4-diisocyanate, 3,3- dimethyldiphenylmethane-4,4-diisocyanate, methaphenylenediisocyanate, triphenylmethanetriisocyanate, 2,4-t0lylenediisocyanate dimer, hexamethylene' diisocyanate, naphthylene-1,5-diisocyanatc). The polymerization is effected at a temperature from room temperature to C, preferably in the presence ofa small amount of a catalytic substance (e.g. ethylenediamine, triethylamine, triethylenediamine, dimethylethanolamine, bis(diethylethanolamine adipate, N,N-dimethyl cyclohexylamine dibutyl tin laurate, dibutyl tin di(2- cthylhexanoate), stannous 2-ethylcaproate, stannous oleate). The ratio ofthe perfluoroalkyl compound [IA] or [[8] and the diisocyanate to be used may be appropriately decided on the kind of the polyurethane to be required. The thus obtained polyurethane has oleophobic and anti-soiling properties and possesses a wide varicty of uses, e.g. the use as coating materials, the use as additives to painting, etc.

Practical and presently preferred embodiments of the invention are illustratively shown in the following Examples. ln these Examples, parts and percent are by weight unless otherwise indicated. Further, various properties such as water-repellency, oil-repellency, stain-removability and anti-soil redeposition in the following Examples are determined by the methods as de scribed below:

1. Water-repellency Measurement is effected according to A.A.T.C.C. Standard Test Method 221952.

2. ()il-repellency Measurement is effected according to A.A.'l'.C.C1 Standard Test Method 118-19661.

3. Stain rcmovability A test cloth is put on a blotting paper extended evenly, and drops ofliquid paraffin is admixture with purple dye Waxoline Purple AS" (manufactured by l.C.l., England) are added dropwise onto one place of the test cloth, which is covered with a polyethylene film. The test cloth is pressed by 2.27 kg of poise for a minute, which is removed. The excess of the liquid paraffin is wiped off with a cotton cloth. The test cloth is allowed to stand for 12 hours and laundered.

Laundering is effected with a drum side-rolling automatic washing machine (manufactured by Sakata Kiko Co., Ltd). To cloths (300 g) including the test cloth, there are added water (15 L) warmed at 45C and a conventional cleaning material (eg Kao Big (made by Kate Soap Co., Ltd.)) (38 g). The resultant mixture is laundered for minutes and washed with water for 2 minutes 3 times. Liquid paraffin-removing degrees are judged by the decolored degree of the purple color. Standard of the decolorization is as follows: same color as that of unlaundered cloth: 1.0; completely decolored case: 5.0; grades between them are judged respectively.

4. Anti-soil redeposition Soil redcposition bath (150 ml) having the composition as defined in the following table is adjusted, stirred at 50C well, and 6 sheets of test cloth (6 X 6 cm) and steel balls are added to the bath. Soiling of the test cloth is effected by turning Launder-O-Meter at 50C for minutes. The soiled cloth is washed with water for 10 minutes and air dried.

The reflectance of the test cloth is measured by using a photometer and the rate of soil redeposition is calculated by the following equation:

(Reflectance of (Reflectance of Stearyl alcohol Continued (Reflectance of (Reflectance of Rate of soil unsoiled cloth) soiled cloth) 5 redeposition Reflectance of unsoiled cloth Composition of soil redeposition bath by weight) Oleyl alcohol (r0052 7. A Solid paraffin (MP. 58 to 60C) 0.0104 "/1 Cholesterol 0,0010 /1 Sodium chloride 0.0208 7! 10 PART A F. X A M Pl E I in a 250 ml volume flask equipped with a thermometer, a stirrer and a cooler. 15

(127.8 g, 0.30 mol), itaconic acid (19.5 g, 0.15 mol), triethylamine (6 g) and hydr'oquinone (1 g) are charged, and the mixture is stirred at 100 to 110C for 6 hours. After confirming the complete consumption of the starting epoxide by gas chromatography, the reaction mixture is distilled under atmospheric pressure to remove triethylamine whereby dark brown solid (153 g) is obtained. The solid is washed with 3 KOH solution at 80 to 85C to eliminate unreacted itaconic acid and, after washing well with pure water, recrystallized from ethyl acetate (500 ml) to give as pale yellow solid (130 g, 0.13 mol) the ester of the formula:

(0P CF(CF CH fHCH OOCCH Elementary analysis. Calcd.: F, 58.04 70; C, 29.32 0, 9.78 40 Found: F, 56.88 C, 30.03 0, 9.53 Infrared absorption spectrum:

3500 (OH), 1720 (fi1-O),

ll-l300 and 980 (fluorinated alkyl), 1650 (-C=C) cm EXAMPLE 2 50 In a 250 ml volume flask equipped with a thermometer, a stirrer and a cooler,

(cF cF(cF cF cH qH;:H

[n 3-7; consisting of 50 of the compound (11 3),

31 of the compound (n =4), 12 of the compound (n 5), 4 of the compound ()1 6) and 3 72 of the compound (n =7)] (125 g, 0.2 mol), maleic acid (11.6 g, 0.1 mol), triethylamine (4 g) and hydroquinone (0.5 g) are charged, and the mixture is stirred at 85 to 90C for 6 hours. After confirming the complete consumption of the starting epoxide by gas chromatography, the reaction mixture is distilled under atmospheric pressure to remove triethylamine whereby dark brown viscous material (137 g) is obtained. The solid is recrystallized from ethyl acetate (300 ml) to give the ester as plase yellow wax solid (134.9 g, 0.091 mol). M P to 83C.

Infrared absorption spectrum:

3350 .(QH). 1725 Pa 4.

1150-1250 and 980 (fluorinated alkyl) cm EXAMPLE 3 As in Example 1,

(CF CF(OF CF CH C H;!H

[11 3-7; consisting of 50 "/1 of the compound (n 3), 31 "/1 ofthe compound (n =4), 12 "/r of the compound (11 5), 4% of the compound (11 6) and 3% of the compound (n=7)] (95 g, 0.151 mol) is reacted with phthalic acid (12.55 g, 0.0755 mol) in the presence of potassium hydroxide (3 g) at 110 to 130C for 1.5 hours. The product is decolorized with active carbon in trichlorotrifluoroethane to give the ester as white solid (102 g, 0.0715 mol). M.P. 66 to 70C.

EXAMPLE 4 As in Example 1,

H(CF CH CHCH (85.6 g. 0.239 mol) is reacted with terephthalic acid (19.8 g, 0.119 mol) in the presence of triethylamine (6.0 g) at 110 to 120C for 3 hours to give the ester (96 g. 0.108 mol). I

EXAMPLE 5 As in Example 1,

(C1- QF(CF CH C\H/CH (127.8 g. 0.30 mol) is reacted with citric acid (19.2 g, 0.15 mol) in the presence oftriethylamine (2 g) at 100 to 110C for 6 hours. Recrystallization of the product from ethyl acetate affords as pale yellow solid (128 g) the ester of the formula:

M.P. 35 to 37C.

Elementary analysis. Calcd.: F, 58.17 C, 29.39 0, 10.88 Found: F, 57.95 C, 29.78 0, 11.03

infrared absorption spectrum:

3500 H). 1720 (--c-o-),

1150-1300 and 980 (fluorinated alkyl) cm EXAMPLE 6 As in Example 1 3350 (O 1725 v z-o 1150-1250 and 980 (fluorinated alkyl) cm EXAMPLE 7 As in Example 1,

(cF cF(cF eF cH c\:/ct1

[n 3-9; consisting of 50 of the compound (n 3), 31% of the compound (n =4),12 of the compound ()1 5), 4 of the compound (n 6) and 3 of the 'compound (n 7)] g, 0.151 mol) is reacted with trimellitic acid (8.7 g, 0.0252 mol) in the presence of potassium hydroxide at to 130C for 3.5 hours. The product is decolorized with active carbon in trichlorotrifluoroethane to give the ester as pale brown solid (98 g). M.P. to C.

EXAMPLE 8 (85.6 g), 0.239 mol) is reacted with alginic acid (degree of polymerization, 70 to 42 g) in the presence of potassium hydroxide (2 g) at 110 to 120C for 6 hours. The pale brown product (125 g) is dissolved in trifluorotrichloroethane, and the resultant solution is portionwise added to water. The precipitate is collected to give the ester as white solid (80 g). In the infrared absorption spectrum, no absorption on a carboxyl group is seen and the absorption of ester is found.

EXAMPLE 9 As in Example 8,

(21.6 g) is reacted with polyacrylic acid (degree of polymerization, 300 to 500; 30 g) in the presence of triethylamine (1 g) to give the ester as pale brown solid (50 g). By the infrared absorption spectrum, it is confirmed that almost all of the carboxyl groups present in the polyacrylic acid are esterified.

EXAMPLE 10 (n 39; average molecular weight, ca. 620) (124 g) and triethylamine (2.0 g) are charged, and the mixture is heated at 90 to 100C for 4 hours. After confirming the complete consumption of the epoxide by gas chromatography, the reaction mixture is cooled and washed with water to give the condensate.

The condensate (50 g), an emulsifier (8 g) obtained by the reaction between dimethyldodecylamine and acetic acid in a molar ratio of 1:3, polyethylene glycol octyl nonyl ether (H.L.B. 18.5) (1.5 g) and ethylene glycol (2.5 g) are charged in a homogenizer and treated for 10 minutes. After addition of hot water (25 g) of 80C. the mixture is treated for 10 minutes. Hot water (25 g) of 80C is further added, and the resultant mixture is treated for minutes to give a dispersion of high stability.

The dispersion (1.3 g) is diluted with pure water (98.7 g). and 6 sheets of cloth made of polyethylene terephthalate fiber and cotton fiber (65:35) are immersed therein for 1 minute and dried at 80C for 20 minutes. Three sheets of them are subjected as such to the tests for oil-repellency. stain removability and antisoil redeposition. Other three sheets are laundered and then subjected to the tests as above. The results are shown in the following table:

Table 1 Oil Stain Anti-soil repelleney removability redeposition Before laundering 7 5 l0 After laundering 6 4.5 8.5

EXAMPLE 11 As in Example 10, HOOCCH=CHCOO(CH CH O),, OCCH=CHCOO(CH CH O),,OCCH=CHCOOH [Nn 4-140; average molecular weight, ca. 4000) (420 g),

(106 g) and triethylamine (2.3 g) are reacted to give the condensate. The condensate is treated in a homogenizer to give a yellowish brown emulsion having a solid concentration of 35 The emulsion is diluted with water to make 1 concentration, and a cloth made of polyethylene terephthalate is immersed therein and dried. The oil-repellency, stain removability and antisoil redeposition ofthe cloth are shown in the following i EXAMPLE 12 In a 500 ml volume flask.

[n 3-9; consisting of 50 of the compound (n 3).

31% of the compound (n =4),12 of the compound (n 5), 4 of the compound (n 6) and 3 71 of the compound (n 79)] (175 g, 0.15 mol) and toluene (300 ml) are charged, and tolylenediisocyanate (26 g, 0.15 mol) and triethylamine (0.5 g) are added thereto. The resultant mixture is heated while refluxing for 1 hour and the solvent is removed by distillation under reduced pressure to give the polyurethane as yellowish brown, transparent resin (198 g). The polyurethane is not softened even at 120C and can be broken into small pieces when struck with a wooden hammer.

A cloth made of polycapramide fiber is immersed in 1 solution of the polyurethane in a mixture of 90 of trifluorotrichloroethane and 10 "/1. of acetone and dired at room temperature. The cloth shows 10 in water-repellency and 10 in oil-repellency.

EXAMPLE 13 (n 38) (6.8 g, 0.0045 mol), tolylenediisocyanate (0.8 g, 0.0045 mol) and triethylamine (0.1 g) is heated at C while stirring and then allowed to stand at room temperature for 3 days to give the polyurethane as yellowish brown, transparent resin. The polyurethane is not softened even at 120C and can be broken into small pieces when struck with a wooden hammer.

A cloth made of cotton fiber is immersed in 1 solution of the polyurethane in a mixture of 90 7c of trifluoroethane and 10 of acetone and dried at room temperature. The cloth shows 9 in water-repellency and 10 in oil-repellency.

EXAMPLE 14 The ester of the formula: (CF CF(CF CH CH(O- H)CH OOCCH=CHCOOCH C- H(OH)CH (CF CF(CF;,) (l g) is dissolved in acetone (200 ml), the resultant solution is admitted in a sprayer for aerosol and a mixture (200 ml) of dichlorodifluoromethane and trichlorofluoromethane (:25 by weight) is charged therein to prepare an aerosol type composition.

The aerosol type composition is sprayed on a lilter paper, and the paper is dried at room temperature for several minutes. When a mixture of water and kerosene is placed on the paper. only water passes through at once and kerosene is retained thereon. Even after 2 days. kerosene does not pass through the paper. The passed water is transparent and odorless and contains no kerosene.

EXAMPLE 15 EXAMPLE 16 The ester of the formula: (CF;,) CF(CF CF ),,CH C- H(OH)-CH OOCCH=CHCOOCH C- l-l(OH)CH (CF CF ),,CF(CF [n 3-7; consisting of 54 7! of the compound (n 3), 28 of the compound (n 4), l2 7: of the compound (n 5), 4.5 of the compound (n =6) and L5 7( ofthe compound (n =7); M.P. 82C] (1 g) is dissolved in acetone (100 ml). A porous sheet of asbestos containing a binder of polyvinyl alcohol is treated with the resultant solution and dried at room temperature. When a mixture of water and n-octane is placed on the sheet, only water passes through the same.

EXAMPLE 17 The ester of the formula:

cs cs cH cH(on)ca ooc7 cooca cmomca wa (l g) and the ester of the formula:

CF (CF CH CH (Oll) CH OOCCH C=CH cloth.

EXAMPLE 18 An end of a cylinder is covered with a sheet of ashestos obtained in Example 16 and the other end is covered with a non-fabric cloth made of polytetrafluoroethylene. A dry cleaning waste liquor consisting of trichloroethylene and water is introduced into the cylinder at the central part through a pump so that water is obtained from the end covered with the asbestos sheet and trichloroethylene from the other end. No material change in the separation effect of the cylinder is seen even after used for 7 hours per day in a period of 1 month.

EXAMPLE 19 Six sheets ofa cloth made of polyethylene terephthalate fiber and of rayon fiber (80:20) are immersed in a solution of the ester of the formula: (CF;,) CF(CF CF ),,CH CH(OH- CH ()()CCH=CHCOOCH C- H(OH)CH(CF CF ),,CF(CF,,) [n 39; consisting of 50 of the compound (n 3), 31 ofthe compound (n =4), 12 ofthe compound (n =5), 4 7o ofthe compound (n 6) and 3 ofthe compound (n 7-9)] (I g) in a mixture of acetone (10 ml) and trichlorotrifluoroethane (190 ml) and dried at room temperature for about 1 hour. Three sheets ofthem are subjected as such to the tests for oil-repellency, stain removability and anti-soil redeposition. Other three sheets are laundered and then subjected to the tests as above. The results are shown in the following table:

Fabrics made of polyethylene terephthalate fiber and of polycapramide fiber are immersed in a solution of the ester of the formula: (CF CF(CF CF ),,CH CH(- OH)CH OOCCH=CHCOOCH CH- (OH)CH(CF CF ),,CF(CF [n 3-9; consisting of 50 of the compound (n 3). 31 of the compound (n 4),12 of the compound (n =5), 4 of the compound (n =6) and 3 ofthe compound (n 7-9)] (1 part by weight) in a mixture parts by volume) of acetone and trichlorotrifluoroethane (5:95 in volume ratio), dried in atmosphere and subjected to the tests for oil-repellency, stain removability and anti-soil redeposition. The results are shown in the following table:

laundering 7 The use of an aqueous dispersion of the said ester (1 g) in a mixture of sodium dodecylbenzenesulfonate (0.25 g), acetone (0.6 g) and water (98.15 g) in place of the above employed treating solution imparts also the same advantageous properties as above to fabrics.

The results ofthe tests carried out using known trcating agents for fabrics made of polyethylene terephthalate fiber are shown in the following table:

Cloths made of polyethylene terephthalate fiber and cotton fiber (65:35) are immersed in a solution of one of the following compounds:

a. Terephthalic acid diester EXAMPLE 22 The ester of the formula: (CF CF(CF CF ),,CH CH(OH)-CH OOCCH=CH [n 3-7; consisting of 54 %'of the compound (n 3), 28 of the compound (n =4), 12 of the compound (n 5), 4.5 of the compound (n 6) and 1.5 of the compound (n 7)] is polymerized using C, H N(CH acetate as an emulsifier, and the resul tant polymer is adjusted to a 15 aqueous emulsion (hereinafter referred to as Emulsion I").

The ester of (CF CF(CF CF ),,CH CH(OH- CH OOCCH=CHCOOCH C- H(OH)CH (CF CF ),,CF(CF [n 37; consisting of 5 4 of the compound (n 3), 28 of the compound (n 4), l2 of the compound (n 5), 4.5 /o of the compound (n =6) and 1.5 ofthe compound (n 7); MP. ca. 82C] is emulsified with C, H ,-,N(CH;,) acetate to prepare l5 aqueous emulsion (hereinafter referred to as Emulsion II).

the formula:

b. Itaconic acid diester (CF CF(CF CH CH(OH)CH OOCCH F(CF cu cru OH) CH OOC-C=CH c. Adipic acid diester C F CI-I CH(OH) (II-1 00C CH COOCH CH( OITI) CH C (lg) in a mixture (100 g) of5 by volume of acetone and 95 by volume of trichlorotrifluoroethane, dried in atmosphere and subjected to the tests for oilrepellency, stain removability and anti-soil redeposition. The results are shown in the following table:

Emulsion I and Emulsion II are mixed in ratios as shown in the following table, and the resultant mixture is diluted to prepare a mixture bath of emulsion. Into the mixture bath, bro'ad fabrics made of polyethylene terephthalate fiber and cotton fiber are immersed;

squeezed to a pick-up of 70 with a mangle, dried at 80C for 10 minutes and heated at 150C for 5 minutes. Water-repellency, oil-repellency, stain removability and anti-soil redeposition of the thus treated fabrics are measured. The results are shown in the part (a) of the table.

Table 6 Oil Stain Ammo Besides, the treated fabrics are laundered and then repellency removability rede osition sub ected to the tests as above mentioned. The results are shown in the part (b) of the table. Tere- Before ph thalic laundering 4 4 l5 j g After At the same time, the above treatments are effected laundering 4 4 16 by the method of using the above prepared mixture bath (hereinafter referred to as Prescription A), the ltaconic Before acid laundering 4 3 5 18 method of using the same bath in mixture with 0.2 dlester An ammonium chloride for the total amount of fluorocar- I' lausdering 3 3 18 bons (hereinafter referred to as Prescription B and I B f the method of using the said mixture bath in admixture iplc e ore u acid laundering 7 45 8 w1th I .25 carbamate treating agent Permafresh diester OHM (made by Damippon Ink Chemical Industry Afer Co., Ltd.) and 0.6 zinc nitrate (hereinafter referred laundering 7 4 8 to as Prescription C Table 7 Ratio of Total solid Pre- (a) Before laundering (b) After laundering Emulsions fluoroscripl/Il carbon tion Water Oil- Stain Anti-soil Water- Oil- Stain Anti-soil (volume content in repelrepelremovredeposirepelrepelremovredeposiratio) bath lency lency ability tion lency lency ability tion (weight 0.4 A 5 4 I5 70 3 4 I8 I alone 0.4 B 6 3.5 I7 70 2 3 15 0.4 C I00 6 8.5 18 8O 4 3 l8 Table 7 Continued Ratio of Total solid Pre- (a) Before laundering (b) After laundering Emulsions fluoroscripl/ll carbon tion Water- Oil- Stain Anti-soil Water Oil- Stain Anti-soil (volume content in repelrepelremovredeposirepelrepelremovredeposiratio) at lency lency ability tion lency lency ability tion (weight 0.4 A 50' 7 5 8 6 9 ll alone 0.4 B 50 7 4.5 8 O 7 4.5 9 0.4 C 50 7 4.5 9 50' 7 4.5 9 0.4 A 70 7 5 7 50 7 5 8 l/ l 0.4 B 80 7 5 8 70 7 5 7 0.4 C 80 8 5 8 70 7 5 8 0.4 A 70 7 5 7 50 7 5 l0 2/ l 0.4 B 90 7 5 7 70 7 4.5 8 0.4 C 90 7 5 8 70 7 4.5 9

0.4 A 70 6 5 6 50 7 5 7 H2 0.4 B 70 7 5 8 50 7 5 8 0.4 C 70 8 5 7 7O 7 5 8 0.4 A 80 7 5 l l 50 7 4.5 13 5/1 0.4 B 90 7 4.5 12 70 7 4.5 9 0.4 C 90 7 4.5 12 70 7 4.5 I3

04 A 70 6 5 6 S0 6 5 6 1/5 0.4 B 70 7 5 6 50 7 5 7 0.4 C 70 7 5 8 50 7 4.5 8

0 A 0 0 5 5 0 0 5 7 Untreated 0 B O 0 5 7 0 0 5 8 0 C 0 O 3.5 18 O 0 4.5 l 1 ll! 02 C 80 7 5 5O 7 5 l 1 Commercially available water 0.4 C I00 6 l 65 80 6 l 63 and oil-repellant Commercially available water- 1.0 C 100 0 l 58 70 0 l 62 repellant EXAMPLE 23 As in Example 22, a 1:1 mixture of a aqueous emulsion of CF CF (CF CF ),,CH CH(OH)C- H OOCCH=CH n 3-7; consisting of 54 of the compound (n =3), 28 of the compound (n 4), l2 7r of the compound (n 5), 4.5 of the compound (n 6) and 1.5 of the compound (n 7) with C ,,H N(CH acetate as an emulsifier and a 15 7c aqueous emulsion of (m 15 in average) as an emulsifier is applied to fabrics made of polyethylene terephthalate fiber. When treated according to Prescription C in Example 22 (total solid fluorocarbon content being 0.6 7c the test results on the water-repellency, oil-repellency, stain removability and anti-soil redeposition are shown in the following table:

Table 8 Water- Oil- Stain Anti-soil repellency removabilredeposition Before launder- 70 7 5 5-12 ing After launder- 5O 7 5 8- l3 [n 3-7; consisting ol 54 r of the compound (:1 3), 28 '71 otthc compound (n =4). 12 7k olthc compound (I) 5) 4.5 "/1 of the compound (n 6) and 1.5 of the compound (n 7); MP. 67 to 70C] with EXAMPLE 24 In Emulsion l as described in Example 22, an cmulsion of the diester as listed in the following table is incorporated to make a ratio of 1:1 as solid fluorocarbon, and the resultant mixture is subjected to use according to Prescription C so as to make 0.5 concentration of solid fluorocarbon. The fabrics treated with such mixture show the water-repellency (l), oil-repellency (2),

23 stain removability (3) and anti-soil redeposition (4) given in the table.

oil-repellency, stain removability and anti-soil redeposition of the treated fabrics are as follows:

Before laundering After laundering Diester (3) (4) (l) (3) (4) krooccn cwa I 80 7 5 9 70 7 5 8 RfOOC a v 1 RfOOC-Q-COORf 8O 6 5 ll 50 5 4. 5

R OOCCH CH(OH)CI1 COORf 80 7 5 7 5O 6 5 8 RfOOCCH=CHCOOR 8O 7 5 1O 7O 7 5 12 g 5 y R OOCCH=CHCOORf 7O 7 5 7 5O 6 5 l2 HOOC(CH COOR 70 6 5 15 5O 5 4 5 l8 4 R OOCCH=CHCOORf 7O 6 5 7 5O 5 4.5 ll

In the above table. Rf represents Table 10 (Cl-;,)- -CF(CF CF ),,--CH CH(OH)CH [n 37; consisting of 56 71 of the compound (n 3), 27 of w ter. on. grai Amb il h compoum 4) 14 f th Compound 5) repellency repellency removability redeposition 2 "/1 ofthe compound (:1 6) and l of the compound Before (11 7)], Rf represents launder- 90 7 5 8 CF,-,CF (CF CF ),,CH CH(OH)CH [n 3-7; con- 'gg sisting of 54 7r of the compound (n 3), 28 of the launder- 70 7 5 10 compound (11 4), l2 of the compound (n 5), 5 s /r of the compound (:1 6) and 1 7c of the compound (n 7)], Rf represents and 11f represents CF (CF CH CH(OH)CH EXAMPLE 26 Six sheets ofa cloth made of polyethylene terephthal- EXAMPLE 25 ate fiber and rayon (80:20) are immersed in a solution A 10 '70 solution of the polymer obtained by polymerof the ester of the formula: iZing )C" H OOCC(CH )==CH using azobisisobutyronitrile in a (CFB)2CF(CF2CF2)I1CH2CH(OH)cflzooc 2 mixture Of and acetone ratio) and a solution of 3)2 2 2)n 2 2 3)2 2 2)" 2 2 OOCCH=CH- (CF CF(CF CF CH CH(OH)CH OOC- 2 COOCl-L CH(OH)CH (CF CF ),,CF(CF [n 3-7; consisting of 58 Of he OmP 27 0f ]n 3-9; consisting of 50 of the compound (n 3), th omp n 14 0f the compound 31% of the compound (n =4), 12 0f the compound 2 ofthe compound (n =6) and l ofthe compound (n 5), 4 of the compound (n 6) and 3 7c of the (n 7)] in a mixture of CF ClCFCl and acetone 60 compound (n=7-9)] (1 g) in amixture of acetone (10 (:10 in weight ratio) are mixed together to make the ml) and trichlorotrifluoroethane (190 ml) and dried at ratio of each total fluorocarbon content 1:1. The reroom temperature for about 1 hour. Three sheets of sulting mixture is diluted with CF ClCFCl to make a them are subjected as such to the tests for oilconcentration of 0.5 g of total fluorocarbon content repellency, stain removability and anti-soil redeposiper ml. Fabrics made ofpolyethylene terephthalate 65 tion. Other three sheets are laundered with a solution fiber and rayon fiber are immersed in the said dilution and dried at room temperature. The water-repellency,

of a cleaning material (37 g) in water (15 L) at 45C in an automatic washing machine for 10 minutes 5 25 a 26 times, rinsed two times with water for 10 minutes, dried c. Trimellitic acid ester at 80C for 20 minutes and then subjected to the tests l as above. The results are shown in the following table:

COOCH CH(OH)CH (CF CF CF(CF Table I 1 5 COOCH CH(OH)CH (CF CF GB (CF9 Oil- Stain Anti-soil ll b'l't' d 1 repe ency remova 11y re eposmon CQOCh2CH(OH)Ch2(C1t 2CF2)2CF( CF3)2 llei'urc laundering 7 5 9 10 All y luundgring 4 5 8 d7 Alginic acid completely esterified with CF (CF2)CH CH(OH)CH OH e. Polyacrylic acid ester EXAMPLE 27 Fabrics made of polyethylene terephthalate fiber and OOCH CMOH) Cli (CF CF(CF of polycapramide fiber are immersed in a solution of the ester as used in Example 26 (1 part) in a mixture 2' 3 5 (100 parts) of acetone and trichlorotril'luoroethane (5:95 in volume ratio), dried in atmosphere and subjected to the tests for oil-repellency. stain removabtlity 1 g) in a mixture 100 g) -"5 b volume f acetone and anti-soil redeposition. The results are shown in the and 95 by volume f i hj t ifl th dried following mhlei in atmosphere and subjected to the tests for oilrepellency, stain removability and anti-soil redeposition. The results are shown in the following table:

Table Table 3 Oil- Stain Anti-soil Oll- Slam Anti-soil repellency removablmy redepobmon repellency removability redeposition Poly- Before Bet-Ore fi 7 8 Mellitic launder- 4 3.5 l5 fiillesm llfier fabric Ilggnder- 7 4.0 7 !aunder 4 4 16 Before mg Polylaunder- 7 4.5 8 L335 Before cflpmmide Pentanelaunder- 4 4 l8 ing tetraing f b i Afl curboxylic After l d 7 4 5 7 40 acid launder- 3 4 l8 ing polyester mg Trimel- Before litic launder- 7 5 8 mg The use of an aqueous dispersion of the said ester (1 ac d After g) in a mixture of sodium dodecylbenzenesulfonate lf 7 X (0.25 g), acetone (0.6 g) and water (98.15 g) in place Alginic Bef re of the above employed treating solution imparts also la 7 l5 l the same advantageous properties as above to fabrics. compkw Afgler ly estelaunder- 7 4,5 13 rified ing Before EXAMPLE 28 Polylaunder 7 5 I2 l' Cloths made oi polyethylene terephthalate fiber and 1C mg After of polycapramide fiber are immersed in a solution of ester launder- 7 4.5 12 one of the following compounds: mg

a. Meilitic acid polyester [H(CF CH2C ]6 b. l,3,3,5Pentanetetracarboxylic acid polyester PART B EXAMPLE I (CF5)2CF(CF2)4CH2CH(OH)CH2OOC CH2 In a 300 ml volume flask equipped with a termomel ter, a cooler and a stirrer,

Elementary analysis. Calcd.: C, 32.05 H, 2.67 F, 60.27 N, 2.34 Found: C, 32.60 H, 2.55 F, 60.5 N, 2.4

The tertiary amine (l g) is dissolved in acetone (100 ml), and a broad cloth made of polyethylene terephthalate fiber and cotton fiber is immersed therein and dried. The resultant cloth shows 70 in waterrepellency and 6 in oil-repellency.

The above prepared tertiary amine (20 g) and acetic acid (6 g) are put in a 50 ml volume beaker, and the resulting mixture is stirred at 40C for 10 minutes. By the infrared absorption spectrum and the elementary analysis, the production of the acetate of the said tertiary amine is confirmed.

The acetate is dissolved in water to make 1 aqueous solution. A broad fabric made of polyethylene terephthalate fiber and cotton fiber is immersed in the solution, squeezed to give a pick-up of 100 dried at 80C for 10 minutes and then heated at 150C for 5 minutes. The cloth shows 70 in water-repellency and 6 in oilrepellency.

EXAMPLE II In a 200 ml volume flask equipped with a thermometer, a stirrer and a cooler,

(150 g, 0.28 mol), CH (CH NH (38.2 g, 0.14 mol) and triethylamine (2 g) are charged, and the resultant mixture is stirred at 100 to 115C for 5 hours. After removal of triethylamine under reduced pressure, the resultant pale brown solid (183 g) is recrystallized from benzene to give the tertiary amine of the formula:

Elementary analysis. Cacld.: C, 37.99 H, 3.69 F, 54.40 /c; N, 1.05 Found: C, 38.2 H, 3.6 F, 53.9 71; N, 1.1

The tertiary amine (1 g) is dissolved in a mixture of trichlorotrifluoroethane (90 ml) and acetone ml). A cloth made of polyethylene terephthalate fiber and cotton fiber is immersed in the solution and dried. The cloth shows 90 in water repellency and 7 in oilrepellency.

EXAMPLE 111 In a 1000 ml volume flask equipped with a thermomctcr, a stirrer and a cooler,

[n 3-7; consisting of 52 of the compound (n 3), 25 of the compound (n 4), 14 of the compound (11 5 6 of the compound (n 6) and 3 of the compound (21 7)] (300 g, 0.51 mol), pentaethylenehexamine (13.5 g, 0.057 mol) and difluorotetrachloroethane (400 g) are charged, and the mixture is stirred at to C for 8 hours. After removal of difluor'otetrachloroethane by distillation under reduced pressure, there is obtained the condensate as pale brown, hard solid (311 g).

EXAMPLE 1V As in Example 10, H NCH CH CH O(CH C- H O),,CH CH CH NH (n 3-140; average molecular weight, 290) (32 g) and or cacn CF3(CF l Table 1 Oil- Stain Anti-soil repellency removability redeposition Before laundering 7 5 l 1 After laundering 5 4 9 EXAMPLE V The condensate (86.5 parts) obtained in Example IV and acetic acid (13.5 parts) are dissolved in water to make a solid concentration of 0.75 g per 100 ml. Fabrics made of polyethylene terephthalate fiber and polycapramide fiber are immersed in the solution, dried and heated at C for 5 minutes. The oilrepellency, stain removability and anti-soil redeposition of the fabrics are shown in the following table:

ing

A cloth made of polyethylene terephthalate fiber and cotton fiber is immersed in a solution of (CF CF(CF soil redeposition. The other portion is washedS times with the solution of a cleaning material (37 g) in water (15 L) at 45C in an automatic washing machine for 10 minutes, rinsed 2 times with water for 10 minutes, dried at 80C for 20 minutes and then subjected to the tests 2)3 2.- 2 2 5)2 P in acetone 5 as above. The results are shown in the following table:

Table IV Water- Oil- Stain Anti-soil repellency repellency removability redeposition Poly- Before ethylene laundering 8O 7 5.0 8 terephthalate After fabric laundering 70 7 5.0 7 Ply- Before caprlaundering 80 7 5.0 8 amide After fabric laundering 8O 7 5.0 7

(100 parts) and dried in atmosphere. Another cloth made of the same fibers as above is immersed in 1 aqueous solution of the acetate ofthe said amine, dried at 80C and treated with heat for minutes. These treated cloths are subjected to the tests for waterrepelleney, oil-repellency, stain removability and rccontaminating rate. The results are shown in the following table:

(5 The use of an aqueous dispersion of the free amine g) produced in Example lll in a mixture ofdimethyloctadecylamine acetate (2 g), acetone (t g) and water (78 g) in a place of the above employed treating solution imparts also the same advantageous properties as above to fabrics.

The results ofthe tests carried out using known treating agents for fabrics made of polyethylene terephthalate fiber are shown in the following table:

Table V Water- Oil- Stain Anti-soil repellency repellency removability redeposition Polymer Before of perlaun- 90 7 2 5O fluorodering alkanesulfonyl- After acryllaun- 80 7 2 67 amide dering Copolymer Before of ethyllaun- 0 0 5 l l acrylate dering and After acrylic launderacid ing 0 0 3 12 Table III What is claimed is:

l. A compound of the formula: Treating Water- Oil- Stain Anti-soil a ent revllme' re ellenc' removabilitv rede osition l P l P [RfCH CH(OH)CH OOC],,,O Free 0 6 s X wherein Rf is a perlluoroalkyl group, an whydro- Acid perfluoroalkyl group or an w-chloro-perfluoroalkyl ga i 0 5 8 group having 4 to 20 carbon atoms, 0 is (CH EXAMPLE VII The product (50 g) obtained in Example III is added to glacial acetic acid (10 g), and the resultant mixture is agitated while heating at C whereby the acetate soluble in water is yielded. In a 1 solution ofthe acetate in water, there is immersed a cloth made of polyethylene terephthalate fiber or of polycapramide fiber, and the cloth is squeezed to remain about 80 by weight of the solution to the amount of the cloth, dried at 80C for 20 minutes and then heated at C for 5 minutes. The cloth is separated into two portions, of which one is subjected as such to the tests for waterrepellency, oil-repellency, stain removability and anti- CH=CH, or C ,-H,,-, in which p is an integer of 1-4 and m is 2.

. 2. The compound of claim 1 in which Q is CH =C- 3. The compound of claim 1 in which Q is C ,-H

4. The compound of claim 1 in which 0 is (CH wherein p is an integer of 1-4.

5. The compound of claim 4 in which p is 4. 

1. A compound of the formula: (RfCH2CH(OH)CH2OOC)mQ wherein Rf is a perfluoroalkyl group, an omega -hydro-perfluoroalkyl group or an omega -chloro-perfluoroalkyl group having 4 to 20 carbon atoms, Q is -(CH2)p-, -CH CH-, or -C6H4-, in which p is an integer of 1-4 and m is
 2. 1. A COMPOUND OF THE FORMULA:
 2. The compound of claim 1 in which Q is -CH2 CH2-.
 3. The compound of claim 1 in which Q is -C6H4-.
 4. The compound of claim 1 in which Q is -(CH2)p- wherein p is an integer of 1-4. 